The invention concerns amino-aldehyde-phosphate resins and copolymer and compositions. The invention also concerns their preparation and use. These amino-aldehyde-phosphate resin and copolymers are useful to produce flame retardant resins for use as plastic sheet, molding resins, coating agents, adhesive, casting resins, flame retardant lamates, binder and flame retardant powders.
Aminoplasts have been produced for many years, but the production of amino-aldehyde-phosphate resins and copolymers are novel. The production of clear amino-aldehyde-phosphate resins are novel. The aminoplasts are white and must be cured under heat and pressure whereas the amino-aldehyde-phosphates may be produced as a water based, self cured clear, tough, rigid or flexible resinous film which is flame retarded. Whiteside (U.S. Pat. No. 4,968,772) and Austin et al (U.S. Pat. No. 2,244,184) utilized an acid catalyst such as phosphoric acid but they utilized only a sufficient amount to adjust the pH. Whiteside utilized only about 1-2% phosphoric acid in the production of his aminoplast, percentage based on the weight of the aminoplast. This invention utilizes about 20 to 40 percent phosphorus oxyacid based on the weight of the amino-aldehyde-phosphate resin or copolymer.
What is lacking and what is needed are useful, safe and inexpensive flame retardant amino-aldehyde-phosphate resin. What is additionally lacking are amino-aldehyde-phosphate copolymers which are water based and upon drying forms a self cured clear, tough, rigid or flexible resinous film which is flame retarded. What is lacking and what is needed are useful, safe and inexpensive flame retardant amino-aldehyde-phosphate resinous powders and compositions for use as flame retardant in plastics and natural products.
In one aspect, the invention comprises of the flame retardant amino-aldehyde-phosphate resin. Another aspect of the invention is the amino-aldehyde-phosphate copolymers and compositions. Another aspect of the invention is a process to prepare an amino-aldehyde-phosphate resin by mixing, selectively heating, and reacting the following components at ambient or elevated temperature and at ambient or lowered pressure and in a molar ratio of amino:aldehyde:phosphorus oxyacid of 1-2;1-2:0.5-1:
A) amino compound
B) aldehyde
C) phosphorus oxyacid
F) water, 0 to 200 percent by weight, percentage based on weight of amino compound; under conditions sufficient to prepare the amino-aldehyde phosphate resin. The components may be mixed in any suitable manner at ambient pressure, they may be mixed simultaneous or the amino compound and aldehyde may be mixed and heated to 50-75 degree C., then phosphorus oxyacid is added and reacted to produce a resinous powder or the phosphorus oxyacid is mixed and reacted with the amino compound or aldehyde compound, then the components are mixed together and reacted to produce an amino-aldehyde-phosphate resin. The components may be heat to just below the boiling point of the components when necessary to speed up the reaction and cure the resin. When excess water is present the mixture may be heated under reduced pressure to remove the excess water. The resin may be produced at ambient temperature and pressure.
In another aspect of the invention is a process to prepare the amino-aldehyde-phosphate copolymers, comprising mixing, heating and reacting the following compounds at ambient or elevated temperature and at ambient or reduced pressure and in a ratio of amino+organic compound:aldehyde: phosphorus oxyacid of 1-2:1-2:0.5-1:
A) Amino compound
B) Aldehyde
C) phosphorus oxyacid
D) organic compound that will react with amino compound, aldehyde and/or phosphorus oxyacid, in the amount of 0 to 100 percent, percentage based on the weight of amino compound;
F) water, in the amount of 0 to 200 percent by weight, percentage based on weight of the amino compound;
under conditions sufficient to prepare the amino-aldehyde-phosphate copolymer. Phosphorus oxyacid is mixed and/or reacted with the amino compound and/or aldehyde and/or the organic compound (component D), the components are mixed at ambient or elevated temperature, at ambient or reduced or elevated pressure, and reacted.
In another aspect of the invention is a process to prepare the amino-aldehyde-phosphate resin, comprising of mixing, heating and reacting:
A) amino compound
B) Aldehyde
C) phosphorus oxyacid
E) filler, in the amount of 0 to 200 percent, percentage based on weight of amino compound;
F) water, in the amount of 0 to 200 percent, percentage based on weight of amino compound;
under conditions sufficient to prepare the amino-aldehyde-phosphate. The phosphorus oxyacid is mixed and/or reacted with the amino compound and/or aldehyde then the components are mixed and components A, B and C are reacted.
Another aspect of this invention is to produce a flame retardant compostion by apply the amino-aldehyde-phosphate resin and/or amino-aldehyde-phosphate copolymer and/or amino-aldehyde-phosphate composition into or on a flammable organic material.
Any suitable amino compound and its salts with free xe2x80x94NH2 radicals may be utilized that will react with an aldehyde. Suitable amino compounds, include, but not limited to, urea, partially hydrolyzed urea condensate, buiret, cyanuric acid, cyamelide, melamine, melamine cyanurate, dicyandiamide, guanidine, cyanoguanidine, aminoguanidine, urea-amino condensate such as urea-melamine condensate, urea-dicyandiamide condensate, urea-guanidine condensate, urea-aminoguanidine condensate, aminophosphates with free xe2x80x94NH2 radicals such as triaminophosphates and diaminophosphates, aminoborates, urea-polyamine condensates, urea-polycarbolic acid condensates, urea-propylene oxide condensates, urea-polyalcohol condensates, urea condensate salt of phosphorus oxyacid with free xe2x80x94NH2 radicals and mixtures thereof. Urea and urea condensates are the most preferred amino compound. Amino compounds are utilized in an amount to produce an amino: aldehyde:phosphate molar ratio of 1-2:1-2:0.5-1.
Suitable aldehydes include, but not limited to, formaldehyde, paraformaldehyde, acetoaldehyde, butyraldehyde, chloral , and other alkyl aldehydes, furfural, benzyl aldehyde acrolein aldehyde, and other aromatic aldehydes. The aldehyde is utilized in an amount to produce an amino:aldehyde:phosphate molar ratio of 1-2:1-2:0.5-1.
Suitable phosphorus oxyacid include, but not limited to, Suitable phosphorus compounds include, but not limited to, phosphoric acid, polyphosphoric acid, pyrophosphoric acid, triphosphoric acid, metaphosphoric acid, hydrophosphorous acid, phosphinic acid, phosphinous acid, phosphine oxide, phosphorus trihalides, phosphorus oxyhalides, phosphorus oxide, salts of phosphoric acid with free hydrogen radicals such as mono-metal dihydrogen phosphates, amino dihydrogen phosphate, amine dihydrogen phosphate and alkali metal dihydrogen phosphate, halogenated phosphate-phosphite and their halides, organic phosphonates, phosphites, phosphates and phosphonate esters and acids and mixtures thereof. Phosphoric acid is the preferred phosphorus oxyacid. The phosphorus oxyacid is utilized in an amount to produce an amino:aldehyde:phosphate molar ratio of 1-2;1-2:0.5-1.
Any suitable organic compound that will react with any of the components, amino compound, aldehyde and/or phosphorus oxyacid may be used in this invention such as, but not limited to, amines, polyamines, phenol compounds such as phenol, cresol, aminophenol, quinones, aniline, Bisphenol A and resorcinol, vinyl acetate, polyvinyl alcohol furfuryl alcohol, epoxy resins, polyepoxy compounds, polyamides, acetyl resins, acrylic acids, cellulose, carbohydrates, polyisocyanates, lignin, amines, alkylanolamines, polycarboxyl acid and anhydrides, epoxies, polyvinyl acetate, organic isocyanates, imides, amides, sulfamic acid, thiourea, epihalohydrin, thiophenol, ketones, alkyl carbonates, oils, fats, allyl alcohol, alkyl acrylic acids, polyester resins with free xe2x80x94OH or xe2x80x94COOH radicals, sucrose amine polyols, sucrose polyols and mixtures thereof. Phenol is the preferred organic compound. The organic compound is utilized in the amount of 0 to 100 percent, percentage based on the weight of the amino compound.
Any suitable filler maybe used in this invention such as, but not limited to, aminoplasts, amino salts of organic phosphates, phenol-aldehyde resin powder, powdered coke, graphite, graphite compounds, plastic powder, silicates, ceramics, silica, metal oxides, silicates, carbonate, sulphates, phosphate and borates, glass or hollow beads, wood flour, straw fibers, nut shells, ammonium sulfates, amino sulfates, china clay, glass fibers and mixtures thereof. The organic halide flame retardant compounds may also be added as fillers. The filler may be used in the amount of 0 to 200 percent, percentage based on the by weight of amino compounds.
Water may be utilized in the amount of 0 to 200 percent, percentage based on the weight of the amino compound. Aqueous formaldehyde contains 60-70% water and it is advisable to reduce some of the water from the amino-aldehyde phosphate resin. The water can be removed by heating the water based resin under reduced pressure. The water may be removed before the reaction is complete to have a concentration of 60-70% solids.
Any suitable basic or acid compound that will adjust the pH may be used in this invention. Inorganic or organic acid are suitable to lower the pH. Typical acids include trichloracetic, ammonium chloride, toluene-p-sulphonic, hydrochloric, sulfuric, sulphamic and phosphoric acids. Any suitable basic salt forming compound may be used to elevate the pH such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, alkali metal carbonates and mixtures thereof. The basic or acid compound is used in the amount of 0 to 10 percent, percentage based on the weight of the amino compound.
Any suitable plastic resin composition or mixtures thereof and any suitable natural organic material maybe used in this invention and mixtures thereof. These materials may be in the form of a solid, cellular suspension, emulsion or solution. Suitable plastic resin include, but not limited to, vinyl dienes, vinyl-diene copolymers, polyesters, polyester resins, phenoplasts, aminoplasts, polyepoxy resins, polyurethanes, furans, polyamides, polyimides, polycarbonates, homopolymers of such olefins as ethylene, propylene, and butylene; block copolymers, consisting of optional combination of these olefins; polymers of vinyl compounds such as vinyl chloride, acrylonitrile, methyl acrylates, vinyl acetates and styrene; copolymers of the foregoing olefins with vinyl monomers, copolymers and terpolymers of the foregoing olefins, with diene compounds; polyesters such as polyethylene terephthalate, polyester resins; polyamides such as nylon; polycarbonates, polyoxymethylene, silicones, polyethers, thioplasts, polytetrafluoroethylene, polysulfones, vinyidienes, poly(vinyl acet compounds, cyclic unsaturated compounds, urethane-epoxy resins, polyimides, urethane silicates, cellulose nitrate rayon, regenerated cellulose film cellulose acetate, cellulose esters, cellulose ethers, cyanoethyl cellulose, chlorinated rubber and mixtures thereof.
Suitable natural products include but not limited to wood, cellulose, lignin-cellulose, paper, cotton, wool, linen, dammars, copols, other natural resins, rosins, lignin, natural rubber, natural proteins, e.g., soya bean protein, silk, glues, gelatin, etc.; modified cellulose and mixtures thereof. Natural organic material and plastics may be mixed together. The amino-aldehyde-phosphate resin, copolymer or composition may be applied on or in the more flammable material in the amount of 5-40 percent, percentage based on the weight of the amino-aldehyde-phosphate resin or copolymer or composition.
Any suitable metal-containing compound that will accelerate carbonization effect used in this invention increases the amount of carbonization residue after combustion, thereby enhancing the flame retardant effect and may be used in this invention. These compounds include, but not limited to, alkaline earth metal borates such as magnesium borate, calcium magnesium borate and the like, manganese borate, zinc borate, metal oxides of titanium oxide, tin oxide, nickel oxide, zinc oxide and the like, ferrocene, dimethylglyoxime copper, acetyl-acetonatocooper, hydroxyquinoline nickel and the like, zinc thiocarbamate compounds such as zinc dimethylthio-carbamate , zinc di-n-butyidithiocarbamate and the like, mercaptobenzothiazole zinc compounds such as mercaptobenzothiazole zinc and the like, salicyadehyde zinc compounds such as salicylaldehyde zinc and the like, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium magnesium hydroxide, zirconium hydroxide and the like and mixtures thereof. The most preferable compounds are selected from zinc oxide, zinc thiocarbamates, the mercaptobenzothiazole zinc compounds the salicyaldehyde zinc compounds, zinc borate and the alkaline earth metal borates. The are utilized in the amount of 0 to 30 percent, percentage based on the weight of the more flammable material.
Any suitable compound that will reflect heat compound such as titanium oxide may be used in this invention and used in the amount of 0 to 30 percent, percentage based on the weight of the flammable material.
Accordingly, this invention provides a process for the preparation of amino-aldehyde-phosphate resins and copolymers. The components, amino compounds, aldehyde and phosphorus oxyacid may be mixed in any suitable manner, such as adding the phosphorus oxyacid to aldehyde and mixing and/or reacting these components at ambient temperature and pressure or heating up to 50 to 75 degrees C. under elevated pressure, then slowly add the amino compound while agitating at ambient temperature and pressure. The mixture may become opalescent when formaldehyde is the aldehyde if urea is added to fast, but the solution become clear and remains clear when heated. The temperature may be elevated gradually up to about 90 degrees C. to speed up the polymer formation and reduce the extractable aldehyde such as formaldehyde, then the pressure may be reduces to remove excess water. It is preferred that the phosphorus oxyacid be added to both the amino compound and the aldehyde, then mixed and reacted at ambient temperature and pressure. It is preferred that the amino compound and part of the phosphorus oxyacid be placed in one container of a two component mixing machine and the aldehyde and part of the phosphorus oxyacid be place into another container of the mixing machine, then they are mixed together and reacted at ambient or elevated temperature. The phosphorus oxyacid may first be reacted with the amino compound then reacted with the aldehyde at ambient or elevated temperature and ambient pressure thereby producing a resin. An amino-aldehyde-phosphate may be produced as a pre-polymer then additional amino compound may be added to cure the resin.
The molar ratio of the components should be regulated in order for all the aldehyde be reacted with the amino compound and phosphorus oxyacid and the copolymer. The molar ratio of the copolymer and/or amino compound to aldehyde to phosphoric acid is 1-2:1-2.0.5-1.
The amino-aldehyde-phosphate resin produced by the process of this invention when aqueous formaldehyde, urea derivatives and phosphoric acid are used in a molar ratio of amino:formaldehyde: phosphoric oxyacid of about 1:2:0.5 produces a water based clear, tough, flexible resin. When less phosphoric acid is used the resin is less flexible and more brittle.
Other carbonization auxiliaries, carbonization accelerators heat shield materials and fillers may be added with the amino-aldehyde-phosphate resin or copolymer or compositions. Carbonization auxiliaries include phosphorus containing compounds, boron containing compounds, boron phosphate containing compounds, sulfur containing compounds that produce acidic components in the pyrolysis mixture and maybe added in an amount of 0-30 percent, percentage based on the weight of the flammable organic material.
The invention is illustrated by reference to the following examples in which all parts and percentages are by weight.